CN101589185B

CN101589185B - Process for forming unidirectionally oriented fiber structures

Info

Publication number: CN101589185B
Application number: CN2007800499925A
Authority: CN
Inventors: B·D·阿维森; A·巴特纳加; H·G·阿迪夫; R·克莱因; L·L·沃纳
Original assignee: Honeywell International Inc
Current assignee: Honeywell International Inc
Priority date: 2006-11-16
Filing date: 2007-11-15
Publication date: 2012-12-12
Anticipated expiration: 2027-11-15
Also published as: CA2669822C; MX2009005209A; EP2082084B1; ATE505572T1; EP2082084A1; JP2010510398A; CA2669822A1; CN101589185A; IL198680A; WO2008061170A1; IL198680A0; ES2361694T3; JP5543782B2; DE602007013929D1; US8652570B2; US20080118639A1

Abstract

A process for forming a unidirectionally oriented fiber structure formed of high tenacity fibers. A plurality of yarns of high tenacity fibers are supplied, with the yarns being unidirectionally oriented. The yarns are coated with a liquid having a viscosity of about 5 to about 600 centipoises and tension is applied to the yarns. The yarns are passed through a fiber spreading device and the yarns are dried. The yarns are reduced in thickness and increased in width after passing through the fiber spreading device, with the fibers forming the yarns being spread apart, thus providing a relativelythin unidirectionally oriented fiber structure.

Description

Form the method for unidirectionally oriented fiber structures

Background of invention

Invention field

The present invention relates to form the method for the fibre structure that comprises single orientation fibers and based on the composite construction of this fibre structure.

Description of Related Art

Present known multiple unidirectionally oriented fiber structures.These structures comprise the fibers of the many general alignment of extending with the relation of copline roughly.This structure that is formed by high-tenacity fiber obtains significant use in shellproof, structure and other are used.In a general structure, make many oriented fibrous structures form multilayer materials, wherein adjacent layer is orientated each other at a certain angle.Two or more adjacent layers are lamination each other, and makes a plurality of these type of laminate layers form composite construction.

Oriented fibrous structure generally applies or dipping with matrix resin, and matrix resin can be thermoplasticity, thermosetting or elastomer substances.This type of composite construction successfully is used for ballistic-resistant article, like bullet-proof vest, structural panel etc.

Catering to the need provides a kind of inhomogeneity unidirectionally oriented fiber structures of improvement that has, and this fibre structure can make shellproof or structural behaviour is improved.

Summary of the invention

The method that the present invention provides a kind of formation to comprise the unidirectionally oriented fiber structures of high-tenacity fiber, said method comprises:

(a) the many yarns that comprise many high-tenacity fibers are provided, the mutual unidirectional layout of said yarn;

(b) the yarn apparatus is had an appointment 5 apply to the liquid of about 600 centipoise viscosity;

(c) tension force is applied on the yarn;

(d) make yarn pass through the fiber lay down extending apparatus; And

(e) make yarn dry;

Wherein after through the fiber lay down extending apparatus, yarn thickness is reduced, and width is increased, and the fiber lay down that forms yarn is launched, so that the unidirectionally oriented fiber structures of relative thin is provided.

The present invention also provides a kind of formation to comprise the method for the composite fibre structure of one deck list orientation high-tenacity fiber at least, and said method comprises:

(c) tension force is applied on the yarn;

(d) make yarn pass through the fiber lay down extending apparatus;

(e) make yarn dry;

Wherein after through the fiber lay down extending apparatus, yarn thickness is reduced, width is increased, and the fiber lay down that forms yarn is launched, so that the unidirectionally oriented fiber structures of relative thin is provided; And

(f) fibre structure of relative thin is attached on another fibre structure.

The method that the present invention further provides a kind of formation to comprise single orientated yarns of high-tenacity fiber, said method comprises:

(a) yarn that comprises many high-tenacity fibers is provided;

(c) tension force is applied on the yarn;

(d) make yarn pass through the fiber lay down extending apparatus; And

(e) make yarn dry;

Wherein after through the fiber lay down extending apparatus, yarn thickness is reduced, width is increased, and the fiber lay down that forms yarn is launched.

The present invention provides the method for a kind of formation than the uniform fiber carrying material, and said material is provided for the evenly composite product of intended use.Find that the viscosity of liquid is fiber is sprawled raising in yarn key factor.Through fiber is sprawled, unidirectionally oriented fiber structures is thinner, because in yarn, there is fiber still less to be positioned on other fibers.The result is that the non-copline fiber number of fiber band goods reduces, and therefore thin goods are provided.

Because a lot of goods with unidirectional pre-immersion material is processed are processed by the multilayer prepreg that overlaps with different angles, the uniformity of manufactured goods is relevant with the uniformity of unidirectional coating or impregnated tape.In addition, some manufactured goods can through in the composite product of processing more multi-segment strengthen.Fiber is sprawled big more, and layer is thin more, and this will increase the number of plies in the composite product of processing of given weight.This factor to for the multiple application that improves the multi-layer compound structure ballistic performance important, like armor application.

The accompanying drawing summary

Behind following detailed description of preferred embodiments and accompanying drawing with reference to the present invention, will become more abundant to understanding of the present invention, other advantages also become obviously, wherein:

Fig. 1 is the sketch map of the method for manufacturing unidirectionally oriented fiber structures;

Fig. 2 sprawls-curve map of viscosity for the fiber of aromatic polyamide yarn;

Fig. 3 sprawls-curve map of viscosity for the fiber of High molecular weight polyethylene yarn; And

Fig. 4 sprawls-curve map of viscosity for the fiber of PBO yarn.

Detailed Description Of The Invention

According to the invention is intended to, fiber is its length dimension prolate body more much bigger than the lateral dimension of width and thickness.Therefore, term " fiber " comprises monofilament, multifilament, band, bar, staple fibre and other forms of staple, cut staple or the discontinuous fibre etc. with rule or irregular cross section.Term " fiber " comprises multiple any aforementioned or its combination.Yarn is the continuous thigh that comprises a lot of fibers or long filament.The used yarn of preferred the present invention is non-twist, and tangles never in any form.

The cross section of the used fiber of the present invention can be in wide variation very.They can be circle, flat or oval cross section.They also can be for having the one or more rules of stretching out from the linear axes or the longitudinal axis of fiber or the irregular or regular leafy shape cross section of irregular blade.Optimum fiber is circular, the flat or oval cross section of essence, most preferably is the essence circle.

Term used herein " high-tenacity fiber " is meant to have the fiber that is equal to or greater than about 7g/d toughness.Preferred these fibers have by ASTM D2256 to be measured at least about the initial tensile modulus of 150g/d with at least about the energy to failure of 8J/g.In this article, term " initial tensile modulus ", " stretch modulus " and " modulus " are meant flexible modulus, are measured by ASTM 2256 for yarn, are measured by ASTM D638 for elastomer or stroma ground substance.

High-tenacity fiber preferably has the toughness that is equal to or greater than about 10g/d, more preferably is equal to or greater than about 16g/d, even more preferably is equal to or greater than about 22g/d, most preferably is equal to or greater than about 28g/d.

The yarn that in fibrage, uses can be any suitable dawn number, for example about 50 dawn to about 3000 dawn, more preferably from about 75 dawn to about 2000 dawn.More preferably the dawn number of yarn is about 200 to about 2000, and more preferably from about 650 to about 1500 dawn.Most preferably yarn is about 650 dawn to about 1500 dawn.Selection is by considering bulletproof effect and cost determination.Manufacturing is bigger than the spun yarn cost, but but per unit weight produces bigger bulletproof effect.

The number that constitutes the fiber of yarn can be in wide variety, and also depends on the dawn number of required yarn.Yarn can form to about 2000 fibers by about 30, and more preferably from about 90 to about 2000 fibers, most preferably from about 120 about 2000 fibers extremely.Most preferably fiber is the monofilament form.

The high strength fibre that in yarn of the present invention and fabric, uses comprises high orientation high molecular polyolefine fiber, is in particular high-modulus polyethylene fibres and polypropylene fibre, aramid fibre, polybenzoxazole fiber (like polybenzoxazole (PBO) and polybenzothiozole (PBT)), vinal, polyacrylonitrile fibre, polyamide fiber, polyester fiber, liquid crystal copolyester fiber, glass fibre, carbon fiber or basalt fibre or other mineral fibres and rigid rod polymer fiber and composition thereof and blend.The preferred high strength fiber that uses in the present invention comprises polyamide fiber, aramid fibre and polybenzoxazole fiber and composition thereof and blend.Most preferably be high molecular weight polyethylene fiber, aramid fibre and polybenzoxazole fibers and composition thereof and blend.Yarn can comprise the blend of single type fiber or two kinds or more kinds of fibers.In addition, the yarn of formation fibre structure can be identical or different type.

United States Patent (USP) 4,457,985 general discussions this type of High molecular weight polyethylene and polypropylene fibre, the disclosure that this patent is consistent with this paper is attached among this paper by reference.Under poly situation, the fiber that is fit to is at least about the fiber of 150,000 weight average molecular weight, preferably at least about 1,000,000, and more preferably from about 2,000,000 to about 5,000,000.This type of high molecular weight polyethylene fiber can in solution, be spun into (see United States Patent (USP) 4,137,394 with United States Patent (USP) 4,356; 138), or from solvent spinning formation gel structure (see United States Patent (USP) 4,413; 110, German Off.No.3,004,699 with BP 2051667); Perhaps make polyethylene fiber (seeing United States Patent (USP) 5,702,657) through rolling (rolling) and drawing process.Term used herein " polyethylene " is meant main linear polyethylene material; This material can comprise a small amount of chain component or the comonomer that per 100 backbone c atoms are no more than about 5 modification unit; One or more polymeric additives that also can comprise no more than about 50% weight of mixing with it; Like the 1-olefin polymer; Especially low density polyethylene (LDPE), polypropylene or polybutene, contain monoolefine as the copolymer of principal monomer, polyolefin, graft polyolefin copolymer and the polyformaldehyde of oxidation, or the low molecular weight additives that usually adds is like anti-oxidant, lubricant, ultraviolet screening agent, colouring agent etc.

High tenacity polyethylene fibers (being also referred to as extended chain or high molecular weight polyethylene fiber) is preferred polyamide fiber; And by Honeywell International Inc.of Morristown; NewJersey, U.S.A. sells with trade mark SPECTRA

.

According to forming technology, draw ratio and temperature and other conditions, can give these fibers multiple performance.The toughness of polyethylene fiber is at least about 7g/d, preferably at least about 15g/d, more preferably at least about 20g/d, more preferably at least about 25g/d, most preferably at least about 30g/d.Similarly, by Instron tension test machine testing, the initial tensile modulus of fiber is preferably at least about 300g/d, more preferably at least about 500g/d, and more preferably at least about 1,000g/d, most preferably at least about 1,200g/d.

These peaks of initial tensile modulus and toughness can only obtain with solution growth or gel spinning method usually.A lot of long filaments have the fusing point that is higher than the melting point polymer that forms them.Therefore, for example, about 150,000, about 1,000,000 generally has this bulk melting point of 138 ℃ with the High molecular weight polyethylene of about 2,000,000 molecular weight.The high orientation polyethylene filament of processing by these materials have high about 7 ℃ to about 13 ℃ fusing point.Therefore, fusing point increases slightly and reflects and compare the perfect crystalline of long filament and the crystalline orientation of Geng Gao with bulk polymer.

The similar high orientation high molecular weight polypropylene fiber that uses at least about 200,000 weight average molecular weight, preferably at least about 1,000,000, more preferably at least about 2,000,000.Through the technology of the above different document specifies that relate to,, can make this extended chain polypropylene form rationally the fully long filament of orientation especially through the technology of United States Patent (USP) 4,413,110.Since polypropylene for than the polyethylene crystallinity little the material of Duoing and comprise the methyl that dangles, therefore, the general essence of the toughness values that available polypropylene obtains is lower than poly analog value.Therefore, the toughness that is fit to is preferably at least about 8g/d, more preferably at least about 11g/d.Be preferably at least about 160g/d for polyacrylic initial tensile modulus, more preferably at least about 200g/d.Polyacrylic fusing point is generally raise the several years by orientation process, makes polypropylene filament preferably have at least 168 ℃ main fusing point, more preferably at least 170 ℃.The special preferable range of above-mentioned parameter can advantageously be improved the performance of end article.The utilization of the fiber that combines with above-mentioned parameter (modulus and toughness) preferable range at least about 200,000 weight average molecular weight can advantageously improve the performance of end article.

Under the situation of aramid fibre, the suitable fiber that is formed by aromatic polyamides is described in United States Patent (USP) 3,671,542, and the part that said patent is consistent with this paper is attached among this paper by reference.Preferred aramid fibre has the toughness at least about 20g/d, and at least about the initial tensile modulus of 400g/d, at least about the energy to failure of 8J/g, preferred especially aramid fibre has at least about the toughness of 20g/d with at least about the 20J/g energy to failure.Most preferred aramid fibre has the toughness at least about 23g/d, at least about the modulus of 500g/d with at least about the energy to failure of 30J/g.For example, (poly P phenylene diamine terephthalamide) long filament that gathers that has appropriate high-modulus and a toughness values is used in particular for forming ballistic composite.The example is available from the Twaron at 1000 dawn of Teijin

T2000.Other instances are the Kevlar

129 and the KM2 (available from du Pont) at Kevlar

29 and 400,640 and 840 dawn with the corresponding initial tensile modulus with 22g/d of 500g/d and toughness values.Can use the aramid fibre that derives from other manufacturers in the present invention.Also can use the copolymer that gathers (poly P phenylene diamine terephthalamide); (poly P phenylene diamine terephthalamide-paraphenylene terephthalamide 3 like copolymerization; 4 ' oxygen base diphenylamines) (co-poly (p-phenylene terephthalamide3,4 ' oxydiphenylene terephthalamide)).In the present invention implements, also can use by duPont and gather (mpd-i) fiber with what trade name Nomex

sold.

High molecular weight polyvinyl alcohol (PV-OH) fiber with high stretch modulus is described in the United States Patent (USP) 4,440,711 of authorizing people such as Kwon, and the part that said patent is consistent with this paper is attached among this paper by reference.HMW PV-OH fiber should have the weight average molecular weight at least about 200,000.The modulus of useful especially PV-OH fiber should be at least about 300g/d, and toughness is preferably at least about 10g/d, and more preferably at least about 14g/d, most preferably at least about 17g/d, energy to failure is at least about 8J/g.PV-OH fiber with this characteristic can for example pass through United States Patent (USP) 4,599,267 disclosed method manufacturings.

Under the situation of polyacrylonitrile (PAN), the PAN fiber should have the weight average molecular weight at least about 400,000.Useful especially PAN fiber should have preferably at least about the toughness of 10g/d with at least about the energy to failure of 8J/g.Have at least about 400,000 molecular weight, at least about 15 to 20g/d toughness and the most useful at least about the PAN fiber of 8J/g energy to failure, these fibers for example are disclosed in United States Patent (USP) 4,535,027.

The used suitable liquid crystal copolyester fiber of embodiment of the present invention for example is disclosed in United States Patent (USP) 3,975,487,4,118,372 and 4,161,470.

The used suitable polybenzoxazole fiber of embodiment of the present invention for example is disclosed in United States Patent (USP) 5,286,833,5,296,185,5,356,584,5,534,205 and 6,040,050.The polybenzoxazole fiber is buied by Toyobo Co. with trade name Zylon

fiber.

Rigid rod fiber for example is disclosed in United States Patent (USP) 5,674, and 969,5,939,553,5,945,537 and 6,040,478.This fibrid can be buied by MagellanSystems International by trade name M5

fiber.

The group method that forms unidirectionally oriented fiber structures is shown among Fig. 1 (a).Similar approach for example is described in United States Patent (USP) 6,642, and 159 and 5,552,208, the disclosure that these patents are consistent with this paper is attached among this paper by reference.

As shown in Figure 1, yarn 102 provides and through combing station 104 from creel, to form the unidirectional fibre network.Preferably on many yarns 102, apply backward pull with tensioner 103.Tensioner 103 is shown as the part of creel 102, but can be the part at combing station 104, perhaps is positioned at the upper reaches that apply groove 108 in addition.Bring network of fibers into coating groove 108, in applying groove 108, apply or dipping with liquid, this more clearly describes following.Other coating units be can utilize, device (waterfall coater), sprayer, roll etc. are coated with like waterfall.

The network of fibers that applies preferably passes through roller to 110, and roller 110 is extruded excess liq, and fluid composition essence is sprawled between long filament equably.The yarn that makes coating is through fiber lay down extending apparatus 105.Sprawl device 105 and be shown as a pair of rod 107,109 of sprawling.Should be appreciated that, can use the additional rod of sprawling, and can use other to sprawl device.Sprawl device 105 and also can be placed on other positions, for example apply the upper reaches of groove 108.As shown in the figure, can make yarn 102 sprawl rod and pass through for 107 times first, sprawl on the rod 109 second then and pass through.Preferably place the network of fibers of sprawling on the net 106 carrying then, carry net 106 and can be paper or film substrate or Muller's fibers network and preferably can be from any other suitable material of its release.Available nip rolls 114 key-course thickness.The fiber network layer that applies is dry, preferably through first heated oven 112.Perhaps, the network of fibers of coating can be through air drying.In baking oven 112, the fiber network layer (" folk prescription is to the preimpregnation band ") that makes coating is through enough heats, so that the liquid in the coating composition volatilizees from solid.

Sprawl rod 107,109 and be preferably hold-down bars, but they can rotate.Can utilize other to sprawl device, as with the roller of yarn opposite direction rotation or with the yarn equidirectional but with the roller of yarn friction speed rotation.

If desired, can face coat be applied on the top surface of network of fibers, for example material through being fit in spraying station 116 sprayings.It is continuous that face coat needs not to be.It can be dripped by discrete spray and form, and preferably is evenly distributed on the surface of network of fibers.Substitute as what spraying applied, also can through network of fibers with roller (not shown) that the reservoir that contains required coating contact under move and apply face coat, perhaps can use other coating units.If apply second coating, then make network of fibers pass through second heated oven 118, so that evaporating in the coating composition.Available nip rolls 120 will carry net and folk prescription is pulled through system to the preimpregnation band.Can make base material and fixed folk prescription on roller 122, be wound in continuous volume then, and the fibre structure of

nip rolls

120 or 122 pairs of single orientations of winding roller provide tension force to the preimpregnation band.

Tensioner 103 can be the braking model on the creel loose winding axle, or any other suitable tensioner, like the electrical feedback of dish type tensioner, aciculiform tensioner, axle brake, dancer arm tensioner etc.Should be appreciated that, can use other tensioners.

As above indicate, in the method for the invention, when applying yarn, yarn is applied tension force, preferably in whole process, apply.The amount of the tension force that applies depends on the dawn number of type, yarn dawn number, toughness, modulus, elongation, the elasticity of fiber in the yarn, the long filament number of every yarn, every threads, the characteristic and the yarn arrangement of the yarn that will sprawl.Generally need the overall tension force (measuring in last sprawling on the device rod) on each yarn to restrain for about 100 to about 1000, more preferably from about 200 to about 800 grams.Through providing tensioner to serve as backward pull at the technology front end, can change the tension force that gets into fiber, this will change through sprawling the tension force of device, thereby at the tension force of obtaining on the last rod in required tension range.Less fibre damage, low equipment cost and increase operating efficiency need low total tension force.The invention enables in whole system is possible to obtain bigger fiber lay down generate than small tension receiving coil.

A kind of network of fibers broadly described in term used herein " coating ", and wherein independent fiber has continuous base composition layer or on fiber surface, has discontinuous base composition layer around fiber.Under preceding a kind of situation, we can say that fiber is embedded in the base composition fully.Term used herein applies and floods interchangeable use.

Find that the type that is used to apply the liquid of yarn can be in wide variety.Liquid can mixing or blending resin for thermoplasticity, thermosetting, elastomer substances or this type of material.The character of the viscosity ratio liquid of liquid itself is more important.

Preferred coatings liquid also is used for the unidirectional fibre structure as matrix resin, but resinous substrates can apply (for example through applying station 116) in second step.Coating liquid can be solution, suspension, dispersion liquid, emulsion or other physical form, and the solids content of coating composition also can great changes have taken place.

Coating can be formed by the multiple material with required character.In one embodiment, as the material of matrix resin have according to ASTM D638 measure be less than or equal to about 6, the initial tensile modulus (elastic modelling quantity) of 000psi (41.4MPa).More preferably coating have be equal to or less than about 2, the initial tensile modulus of 400psi (16.5MPa).Most preferably coated substance have be equal to or less than about 1, the initial tensile modulus of 200psi (8.23MPa).These resinous substancess are generally thermoplastic properties.It should be noted that all stretch moduluses are measured the drying sample of coating composition.

Perhaps, can select resinous substrates when solidifying, to have high stretch modulus, as at least about 1 * 10 ⁶Psi (6895MPa).The instance of this type of material is disclosed in for example aforesaid U.S. Patent 6,642,159.

Point out that more than coating liquid has about viscosity of 5 to about 600cps, more preferably from about 10 to about 300cps, and most preferably from about 10 to about 250cps.The viscosity that is used as the liquid of coating can change in mode known in the art.For example, can viscosity modifier or thickener be added to coating composition.Perhaps, can change the solids content of coating composition, so that required range of viscosities to be provided.In addition, the temperature of scalable coating composition (heating or cooling) is to provide required viscosity.

Can be with multiple material as coating composition (being preferably the resinous substrates that composite is used).For example, any following elastomer substances capable of using: the polyethylene of polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, polysulfide polymer, polyurethane elastomer, chlorosulfonation, polychlorobutadiene, utilize dioctyl phthalate or at the copolymer of polyvinyl chloride, butadiene-acrylonitrile elastomer, isobutylene-isoprene copolymer, polyacrylate, polyester, polyethers, fluoroelastomer, silicone elastomer, thermoplastic elastomer (TPE), thermoplastic polyurethane and the ethene of other plasticizer plasticizing well known in the art.The instance of thermosetting resin comprises those resins that dissolve in the carbon-to-carbon saturated solvent, solvent such as methyl ethyl ketone, acetone, ethanol, methyl alcohol, isopropyl alcohol, cyclohexane, ethyl acetone and combination thereof.Vinyl esters, styrene-butadiene block copolymer, dially phthalate, phenol formaldehyde resin, polyvinyl butyral resin and composition thereof are arranged in these thermosetting resins, and like aforesaid U.S. Patent 6,642,159 is disclosed.Preferred thermosetting resin comprises the catalyst that at least a vinyl esters, dially phthalate and optional being used to are solidified vinyl ester resin.

One group of preferred substance is the block copolymer of conjugated diene and vinyl aromatic copolymers.Butadiene and isoprene are preferred conjugated diene elastomers.Styrene, vinyltoluene and t-butyl styrene also are preferred conjugated aromatic monomers.Can make the block copolymer hydrogenation that is combined with polyisoprene, to make thermoplastic elastomer (TPE) with saturated hydrocarbons elastomer segment.Polymer can be R-(BA) _xThe simple triblock copolymer of type (x=3-150), wherein A is the block from the polyvinyl aromatic monomer, B is the block from conjugated diene elastomers.A kind of preferred resinous substrates is isoprene-styrene-isoprene block copolymer; Like Kraton

D1107 isoprene-styrene-isoprene block copolymer, derive from Kraton Polymer LLC.

Whether needs " firmly " or the shellproof or other materials of " soft " type according to, resinous substrates can be thermoplasticity or thermosetting substance.

The preferred coatings composition is water-based resin or solvent-based resin.Perhaps, coating composition can provide hot melt to be coated on other materials on the yarn then for wax or heating.In addition, also can powdered rubber be heated into melt, be coated on the yarn then.

After coating composition is applied to yarn, make the high strength fibre network be consolidated into base composition/fiber combinations." fixed " is meant that stroma ground substance and fiber network layer are combined into single integral layer.Can carry out fixed through drying, cooling, heating, pressure or its combination.

The ratio of coating and fiber can according to final use and whether coating will great changes have taken place as matrix resin in the composite bed.The resinous substrates material be preferably fiber and resinous substrates gross weight about 1 to about 98% weight, more preferably from about 5 to about 95% weight, most preferably from about 5 to about 40% weight.

Do not form resinous substrates at coating liquid and under the situation about sprawling, can use other materials but fiber caters to the need.The instance of this type of coating liquid is water and the viscosity modifier or the thickener that are fit to, like starch, polyacrylic acid, polyvinyl alcohol and celluosic resin etc.Spendable other materials are the viscosity solution of oil, adhesive solvent (like glycerine), low concentration high molecular weight material or the solvent with thickener (like cellulosic material) etc.Below provide as an example, rather than the exhaustive list of the material that can in required range of viscosities, use.

As above mention, method of the present invention provides the unidirectionally oriented fiber structures of relative thin." relative thin " is meant that said fibre structure is than thin by not sprawling fibroplastic similar structures.The thickness of preferred each fibre structure is single thread diameter about 5 times to the single thread diameter.The thickness of each layer of unidirectionally oriented fiber structures can be selected according to the number of plies in required final use and the end article.For example, each unidirectionally oriented fiber structures layer can have about 0.35 thickness to about 3 mils (9 to 76 μ m), more preferably from about 0.35 mil to about 1.5 mils (9 to 38 μ m).

According to required final use, the available single orientation supatex fabric that obtains in sandwich construction as one deck.Preferably make one or more other one-way fabrics and said one deck be consolidated into sandwich construction.For example, can overlap through the unit of two one deck structures and form two-layer composite, perhaps overlapping through the unit with three other one deck structures forms four layers of composite.The composite that is formed by fibre structure of the present invention preferably has the fibrage of at least two high-tenacity fibers.

Pantostrat is preferably each other for example with 0 °/90 °, 0 °/90 °/0 °/90 ° or 0 °/45 °/90 °/45 °/0 ° or other required angle rotations.Make these layers be consolidated into multi-ply fibrous structure.The unidirectional array of this rotation is described in for example United States Patent (USP) 4,457,985,4,748,064,4,916,000,4,403,012,4,623,574 and 4,737,402.

Fiber in each adjacent layer can be identical or different, although the fiber in the adjacent layer of composite is preferably identical.

If desired, can make one deck and one or more layers dissimilar layer be combined into required sandwich construction.These other layers can be processed by the high-tenacity fiber of non-woven structure (like the milled cloth) form of woven, knitting or other types.If fibrolaminar fabric is the woven fabric form, then can be any texture pattern, comprise plain weave, twill-weave, satin weave, three-dimensional woven fabric and any several kinds of modification thereof.Plain weave fabric is preferred, more preferably has identical plain weave fabric through yarn count and weft yarn number.Woven fabric can be used on the yarn that warp-wise and broadwise or other directions have different fibers and is made into.

Do not consider the physical form of each fibre structure, preferably the fiber of at least 50% weight is a high-tenacity fiber in each layer, and more preferably the fiber at least about 75% weight is a high-tenacity fiber, and most preferably all fibers of essence are high-tenacity fiber.

According to final use, available one or more plastic films and fibre structure combination are so that reduce the friction between the composite when several composites are placed each other.In the application of for example health protector (body armor), this desirably provides dress more comfortable health protector.Any suitable plastic films capable of using is like the film of being processed by polyolefin.The instance of this type of film is linear low density of polyethylene (LLDPE) film, polyester film, nylon film, polycarbonate film etc.These films can be any desirable thickness.General thickness is about 0.1 to about 1.2 mils (2.5 to 30 μ m), and more preferably from about 0.2 to about 1 mil (5 to 25 μ m), and most preferably from about 0.3 to about 0.5 mil (7.5 to 12.5 μ m).

Known multiple structure is used for the fibre reinforced composites that use at shock resistance and ballistic-resistant article, these goods such as the helmet, panel and vest.The anti-high speed body (like bullet, shell fragment and fragment etc.) of these composite showed different impacts penetrability.For example, United States Patent (USP) 6,268,301,6,248,676,6,219,842,5,677,029,5,587; 230,5,552,208,5,471,906,5,330,820,5,196,252,5,190,802,5; 187,023,5,185,195,5,175,040,5,167,876,5,165,989,5,124; 195,5,112,667,5,061,545,5,006,390,4,953,234,4,916,000,4; 883,700,4,820,568,4,748,064,4,737,402,4,737,401,4,681; 792,4,650,710,4,623,574,4,613,535,4,584,347,4,563; 392,4,543,286,4,501,856,4,457,985 and 4,403,012 has all described ballistic composite, and these composites comprise the high strength fibre of being processed by the for example material of High molecular weight polyethylene, aromatic polyamides and polybenzoxazole.It is said that these composites are pliability or rigidity according to its structural property and used material.

Can fixed folk prescription be cut into discrete sheet to the preimpregnation band, and lay becomes to be used to form the stacking of final use composite, perhaps can make their form assembly precursor, subsequently with the composite of assembly precursor formation final use." composite of final use " is meant complete multilayer materials, can be goods of the present invention, like the helmet or Vehicle protector plate.Arrive like prerequisite, most preferred composite is unidirectional alignment of the network of fibers of wherein each layer and orientation, so that the machine direction in the pantostrat is the composite of 0 °/90 ° of structures.

In one embodiment, two fiber network layer overlap with 0 °/90 ° structures, are molded as the assembly precursor then.Preferably through one of the network segment, the width that makes each section stride another network with 0 °/90 ° orientations is then placed continuously, and two fiber network layer are overlapped continuously.United States Patent (USP) 5,173,138 and 5,766,725 have described continuous overlapping equipment therefor.The continuous double-layer assembly that obtains can twine rolling then, twists in to have spacer material layer between each layer.When preparing to form the final use composite, will roll up expansion, and isolated material will be peelled off.To accomplish section bar and matrix resin is solidified in order to form, then double-layer assembly is cut into discrete sheet, with multiple-level stack, subsequently through overheated and pressure.

The temperature of the molded exposure of network of fibers and/or pressure depend on the type of used high strength fibre.Through (1,030 to 2,760kPa) (preferred about 180 to 250psi (1,240 to 1,720kPa)) and about 104 ℃ of laminations to one two layer assembly of about 127 ℃ of temperature lower mould can be made the final use composite that is used for protective plate to pressure about 150 to 400psi.Through at about 1500 to 3000psi (10.3 to 20.6MPa) pressure and about 104 ℃ of laminations, can make the final use composite that is used for the helmet to one two layer assembly of about 127 ℃ of temperature lower mould.

The characteristic of the unidirectionally oriented fiber structures that is formed by the inventive method is that yarn flattens, and fiber lay down reaches required distance.Through fiber is spread out, fiber has more space to present more flat structure, thereby produces thin fibre structure.For some application, armor application for example, this is very important, because there is less fiber to pile up each other.This makes more fiber be used to prevent that body from penetrating.Thin structure also allows to increase shellproof protection and do not increase the gross thickness of protective clothing etc. with more fibre structure layer.

In order to understand the present invention more completely, unrestricted embodiment below existing the proposition.Concrete technology, condition, material, ratio and the report data of illustrating the explanation principle of the invention are exemplary, and should not be construed as limitation of the scope of the invention.

Embodiment

Embodiment 1-9

The yarn that use is formed by the high tenacity aramid fibre.Yarn has 1000 dawn numbers, and forms (buying as Twaron 1100dtex f1000Type 2000 from Teijin) by 1000 aramid yarns.Yarn is sent into the container that holds coating composition from bobbin.6 ounces of (170 gram) weight are applied on the axle that supplies bobbin.Yarn is immersed coating composition, send into then and sprawl the station, sprawl the station and become by 1 inch (25.4mm) diameter and two stainless steel parallel metal clavates separating 0.29 inch (7.37mm).Yarn is at first sprawled under the device rod first and was sent, and sprawls on the device rod second then and send.Yarn is wrapped on the drum winder that is coated with stripping film.The width of yarn is sprawled rod second and is measured, and tension force was measured before sprawling rod.Tension force keeps when yarn feeds container for paint and make progress through coiler device.

Carry out a series of tests with different coating compositions and different viscosities.Change solid in some cases,, increase viscosity with additive in other cases, and water reduces the viscosity of water-based resin to change viscosity (as in solvent-based resin, like the Kratron/ cyclohexane).Each composition and the fiber of liquid viscosity detection on rod are sprawled.

In embodiment 1 (comparative), do not use liquid, fiber is sprawled in air.In embodiment 2 and 3 (comparative), liquid is respectively water and cyclohexane.In embodiment 4 (comparative), liquid is the rheology modifier (Acrysol

) of water and 0.1 to 1.0% weight.

In embodiment 5; Use Kratron the D1107 SIS of variable concentrations in the cyclohexane, this produces different viscosity.In embodiment 6, liquid be polyurethane resin (Sancure 12929) itself and with 0.1 to 0.4% weight Acrysol

.In embodiment 7, liquid is water base styrene-isoprene-phenylethene resin (Prinlin

B7137AL) and Acrysol

modifier of different amounts.In embodiment 8, liquid is polyurethane resin (Dispercoll

U53) and Acrysol

modifier of different amounts.In embodiment 9, use the oil of different SAE grades.

The result is shown in the following table 1, and table 1 gathers the percentage of solids and the corresponding viscosity of liquid resin.The result also is depicted among Fig. 2 with figure.

Table 1

Embodiment	Liquid	%, composition	Tension force, g	Mean breadth inch (cm)	Viscosity, cP
						1	Air	100	500	0.1282(0.3256)	0.18
2	Water	100	490	0.1226(0.3114)	0.95
						3	Cyclohexane	100	540	0.1239(0.3417)	2.10
4-1	Water+modifier ^a	0.1	620	0.1048(0.2662)	0.98
						4-2	Water+modifier ^a	0.5	600	0.1117(0/2972)	0.99
4-3	Water+modifier ^a	1.0	620	0.1069(0.2715)	1.03
						4-4	Water+modifier ^a	On average	613	0.1078(2738)	1.00
5-1 ⁶	The SIS resin ^b	4.0	560	0.1273(0.3233)	8.0
						5-2	The SIS resin ^b	7.4	520	0.1478(0.3754)	25.3
5-3	The SIS resin ^b	11.5	580	0.1535(0.3899)	78.8
						5-4	The SIS resin ^b	14.5	580	0.1461(0.3711)	173.2
5-5	The SIS resin ^b	17.5	600	0.1371(0.3482)	383.0
						5-6	The SIS resin ^b	21.5	580	0.1240(0.3150)	784.0
6-1	Polyurethane ^c	0.0	640	0.1388(0.3526)	16.5
						6-2	Polyurethane ^c	0.1	620	0.1455(0.3696)	26.0
6-3	Polyurethane ^c	0.2	600	0.1448(0.3678)	41.5
						6-4	Polyurethane ^c	0.3	600	0.1416(0.3597)	68.0
6-5	Polyurethane ^c	0.4	660	0.1355(0.3442)	106.0
						7-1	The SIS resin ^d	0.5	620	0.1421(0.3609)	76.5
7-2	The SIS resin ^d	1.0	620	0.1538(0.3907)	117.5
						7-3	The SIS resin ^e	0	660	0.1579(0.4011)	171.0
7-4	The SIS resin ^e	0.5	600	0.1588(0/4034)	251.5
						7-5	The SIS resin ^e	1.0	620	0.1539(0.3909)	550.0
8-1	Polyurethane ^f	0	660	0.1353(0.437)	7.8
						8-2	Polyurethane ^f	0.1	620	0.1506(0.3825)	11
8-3	Polyurethane ^f	0.2	600	0.1532(0.3891)	14.5
						8-4	Polyurethane ^f	0.3	580	0.1513(0.3843)	26
8-5	Polyurethane ^f	0.4	600	0.1507(0.3828)	28.6
						8-6	Polyurethane ^f	0.6	620	0.1417(0.3599)	83.2
8-7	Polyurethane ^f	0.8	640	0.1402(0.3561)	137
						8-8	Polyurethane ^g	0.2	620	0.1369(0.3477)	204.5
8-9	Polyurethane ^g	0.3	640	0.1334(0.3388)	434.0
						8-10	Polyurethane ^g	0.4	660	0.1330(0.3378)	875.0

Table 1 (continuing)

Embodiment	Liquid	%, composition	Tension force, g	Mean breadth inch (cm)	Viscosity, cP
						9-1	SAE#10	100	600	0.1433(0.3640)	65.0
9-2	SAE#20	100	580	0.1534(0.3896)	125.0
						9-3	SAE#30	100	640	0.1528(0.3881)	200.0
9-4	SAE#40	100	760	0.1443(0.3665)	319.0
						9-5	SAE#90	100	800	0.1423(0.3614)	590.0

Annotate:

A=modifier is Acrysol

RM-8W ethylene oxide carbamate rheology modifier, available from Rohm and Haas.

B=is available from Kraton the D1107 SIS of Kraton Polymers, the percentage by weight in cyclohexane.

c = purchased from Noveon's Sancure 12929 Water-based polyurethane + Acrysol

RM-8W.

d = Prinlin

B7137AL (Kraton

D1107 styrene - isoprene - styrene resin, a water-based dispersion (21% solids)) + Acrysol

RM-8W.

e = Prinlin

B7137AL (Kraton

D1107 styrene - isoprene - styrene resin, a water-based dispersion (35% solids)) + Acrysol RM-8W.

f = from Bayer's Dispercoll

U53 water-based polyurethane (28% solids) + Acrysol

RM-8W.

g = purchased from Bayer's Dispercoll U53 water-based polyurethane (45% solids) + Acrysol RM-8W.

Additive percentage is based on the solids content of resin in the liquid.

SAE=SAE

Legend among Fig. 2 is following: A=air, B=water, C=cyclohexane, D=water and Acrysol, E=Kraton, F=Sancure and Acrysol, G=Prinlin and Acrysol, H=DispercollU53 and Acrysol, I=oil.

Can find, obtain significant fiber with liquid handling aramid fibre and sprawl with scope of the invention viscosity.With air, water and other flowing fluid ratios of not having viscosity of the present invention, promote fiber to sprawl with liquid handling aramid fibre with characteristic of the present invention.

Embodiment 10-15

Use high tenacity polyethylene yarn (1300 dawn were formed by 240 Spectra , 1000 filaments) to repeat embodiment 1-9 available from Honeywell International Inc.The result is shown in the following table 2, and is depicted among Fig. 3 with figure.

Table 2

Embodiment	Liquid	%, composition	Tension force, g	Mean breadth inch (cm)	Viscosity, cP
						10	Air	100	450	0.1968(0.5000)	0.18
11	Water	100	320	0.1433(0.3640)	0.95
						12	Cyclohexane	100	290	0.1500(0.3810)	2.10
13-1	Polyurethane ^a	0.0	390	0.1477(0.3752)	7.8
						13-2	Polyurethane ^a	0.1	370	0.1399(0.3553)	11
13-2	Polyurethane ^a	0.2	460	0.1463(0.3716)	14.5
						13-3	Polyurethane ^a	0.3	390	0.1399(0.3553)	26
13-4	Polyurethane ^a	0.4	440	0.1463(0.3716)	28.6
						13-5	Polyurethane ^a	0.6	420	0.1458(0.3703)	83.2
13-6	Polyurethane ^a	0.8	460	0.1493(0.3792(	137
						14-1	The SIS resin ^b	4.0	360	0.1363(0.3462)	8.0
14-2	The SIS resin ^b	7.4	380	0.1489(0.3782)	25.3
						14-3	The SIS resin ^b	11.5	360	0.1505(0.3823)	78.8
14-4	The SIS resin ^b	14.5	430	0.1480(0.3759)	173.2
						14-5	The SIS resin ^b	17.5	440	0.1463(0.3716)	383.0
14-6	The SIS resin ^b	21.5	450	0.1492(0.3790)	784.0
						15-1	The SIS resin ^c	0.0	520	0.1528(0.3881)	43.0
15-2	The SIS resin ^c	0.5	520	0.1545(0.3924)	76.5
						15-3	The SIS resin ^c	1.0	490	0.1520(0.3861)	117.5
15-4	The SIS resin ^d	0.0	500	0.1504(0.3820)	171.0
						15-5	The SIS resin ^d	0.5	480	0.1473(0.3741)	251.5
15-6	The SIS resin ^d	1.0	480	0.1508(0.3830)	550.0

Annotate:

a = from Bayer's Dispercoll

U53 water-based polyurethane (28% solids) + Acrysol

RM-8W.

B=is available from Kraton

the D1107 SIS of Kraton Polymers, the percentage by weight in cyclohexane.

c = Prinlin

B7137AL (Kraton

RM-8W.

d = Prinlin

B7137AL (Kraton D1107 styrene - isoprene - styrene resin, a water-based dispersion (35% solids)) + Acrysol

RM-8W.

Additive percentage is based on the solids content of resin in the liquid.

Legend among Fig. 3 is following: A=air, B=water, C=cyclohexane, D=U53 and Acrysol, E=Kraton, F=Prinlin and Acrysol.

Can see from above embodiment,,, then use about 5 useful to the viscosity of about 600 centipoise scopes if utilize liquid medium though the high tenacity polyethylene yarn is sprawled the best in air.In liquid, handling yarn especially caters to the need when to the high tenacity polyethylene yarn matrix resin being provided as medium with liquid.

Embodiment 16-18

Be used as PBO yarn (1000 dawn yarns, 1110dtex) the repetition embodiment 1-9 of Zylon

AS A1110T available from Toyobo Co.The result is shown in the following table 3, and is depicted among Fig. 4 with figure.

Table 3

Embodiment	Liquid	%, composition	Tension force, g	Mean breadth inch (cm)	Viscosity, cP
						16	Air	100	450	0.1269(0.3223)	0.18
17	Water	100	370	0.1397(0.3548)	0.95
						18-1	SAE#10	100	540	0.1499(0.3807)	65.0
18-2	SAE#20	100	540	0.1557(0.3955)	125.0
						18-3	SAE#30	100	620	0.1516(0.3851)	200.0
18-4	SAE#40	100	660	0.1524(0.3871)	319.0
						18-5	SAE#90	100	680	0.1475(0.3747)	590.0

Legend among Fig. 4 is following: A=air, B=water, C=oil.

Can find, obtain significant fiber with liquid handling pbo fiber and sprawl with scope of the invention viscosity.Compare with empty G&W, promote fiber to sprawl with liquid handling pbo fiber of the present invention.

Can find that the present invention is through at first applying the method that promotes that high-tenacity fiber is sprawled that provides with the coating composition of certain viscosity scope.Be surprised to find that when the liquid with this range of viscosities applied yarn, fiber was sprawled and obtained promoting.This allows with the thin unidirectionally oriented fiber structures of the yarn manufacturing of sprawling.Therefore, in armor application, for example improve the interaction of body and fiber, thereby increase the bulletproof ability of the end article of processing by several unidirectional plies.Through thinner layer is provided, can more multilayer be provided for identical weight, and the goods of processing there is better ballistic performance.

In addition, apply yarn with the disclosed liquid of this paper and allow fiber to sprawl, thereby reduce fibrous fracture and increase operating efficiency at lower total tension force.

Though described in detail the present invention, should be appreciated that these details needn't be adhered rigidly in strictness, those skilled in the art can expect other variation and modification, these variations and modification all drop in the scope of the present invention of accessory claim qualification.

Claims

1. a formation comprises the method for the unidirectionally oriented fiber structures of high-tenacity fiber, and said method comprises:

(b) said yarn is applied with the liquid with 5 to 600 centipoise viscosity;

(c) when applying said yarn, change the tension force of said yarn, so that the overall final tension force on each yarn is the 100-1000 gram;

(d) make said yarn through the fiber lay down extending apparatus; And

(e) make said yarn dry;

Wherein after through said fiber lay down extending apparatus, the thickness of said yarn is reduced in said coating step (b) back with in that said drying steps (e) is preceding; Width is increased; And the fiber lay down that forms said yarn is launched, be the unidirectionally oriented fiber structures of 9 to 76 μ m so that thickness is provided.

2. the method for claim 1, said method further are included in the step of the said yarn of reeling after the said yarn drying.

3. the process of claim 1 wherein that said high-tenacity fiber is selected from high molecular polyolefine, aromatic polyamides, polyvinyl alcohol, polyacrylonitrile, polybenzoxazole, polyamide, polyester, liquid crystal polyester, glass, carbon, basalt, mineral fibres and rigid rod fiber and blend thereof.

4. the process of claim 1 wherein that said high-tenacity fiber comprises aramid fibre.

5. the process of claim 1 wherein that said high-tenacity fiber is selected from high molecular weight polyethylene fiber, aramid fibre, polybenzoxazole fiber and blend thereof.

6. the process of claim 1 wherein that said high-tenacity fiber has the toughness at least 28 gram/dawn.

7. the method for claim 1, said method are included in during the step (b) to (e) step that said yarn is applied backward pull.

8. the process of claim 1 wherein that said viscosity is 10 to 300 centipoises.

9. the process of claim 1 wherein that said liquid comprises water-based resin, solvent-based resin or hotmelt substance.

10. the process of claim 1 wherein that said liquid comprises polyurethane resin.

11. the process of claim 1 wherein that said liquid comprises viscosity modifier.

12. the process of claim 1 wherein that said tension force is 200 to 800 grams.

13. the process of claim 1 wherein that said liquid comprises solid, said solid is formed for the matrix resin of the said fiber in the said unidirectionally oriented fiber structures.

14. the method for claim 1, said method further comprise the step of the layer overlapping that makes at least two said unidirectionally oriented fiber structures.

15. the process of claim 1 wherein that said fiber lay down extending apparatus comprises that a plurality of fibers sprawl rod.

16. a unidirectionally oriented fiber structures, said unidirectionally oriented fiber structures forms through the method for claim 1.

17. a protector, said protector comprise a plurality of said unidirectionally oriented fiber structures that form through the method for claim 1.

18. a method that forms the composite fibre structure, said composite fibre structure comprise one deck list orientation high-tenacity fiber at least, said method comprises:

(b) said yarn is applied with the liquid with 5 to 600 centipoise viscosity;

(d) make said yarn through the fiber lay down extending apparatus;

(e) make said yarn dry;

Wherein after through said fiber lay down extending apparatus, the thickness of said yarn is reduced in said coating step (b) back with in that said drying steps (e) is preceding; Width is increased; And the said fiber lay down that forms said yarn is launched, be the unidirectionally oriented fiber structures of 9 to 76 μ m so that thickness is provided; And

(f) making said thickness is that the unidirectionally oriented fiber structures of 9 to 76 μ m is attached on another fibre structure.

19. a formation comprises the method for single orientated yarns of high-tenacity fiber, said method comprises:

(a) the said yarn that comprises many high-tenacity fibers is provided;

(b) said yarn is applied with the liquid with 5 to 600 centipoise viscosity;

(d) make said yarn through the fiber lay down extending apparatus; And

(e) make said yarn dry;

Wherein after through said fiber lay down extending apparatus, the thickness of said yarn is reduced, width is increased, and the said fiber lay down that forms said yarn is launched in said coating step (b) back with in that said drying steps (e) is preceding.

20. the method for claim 19, wherein said fiber are selected from high molecular weight polyethylene fiber, aramid fibre and polybenzoxazole fiber and blend thereof.